Composite, porous diaphragm

ABSTRACT

A composite, porous, liquid-permeable article is provided which is a multilayer structure of discrete, bonded layers of porous, expanded polytetrafluoroethylene (EPTFE), which composite has its interior and exterior surfaces coated with a perfluoro ion exchange polymer to render the composite hydrophilic so as to resist gas locking in aqueous media wherein a composite diaphragm made therefrom, may also contain a water-soluble surfactant to assist in initial water penetration into the pores of the composite whereby an improved electrolytic cell is provided having the composite diaphragm as the porous separator in the electrolysis of alkali halide solutions and wherein the diaphragm is also useful as an improved filter medium.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of earlier filed applicationSer. No. 07/344,707, filed Apr. 28, 1989, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a porous, liquid-permeable composite articleuseful as a diaphragm for electrolysis or as a filtering medium.

2. Description of Related Art

In the electrolysis or electrosynthesis of chemical compounds, a porousdiaphragm is often used to separate the anode and cathode compartmentsand the reaction products while permitting the flow of some liquidcomponents from one compartment to another. For example, in theproduction of chlorine and sodium hydroxide from brine, the brine feedflows from the anode compartment through the porous diaphragm to thecathode compartment and then is discharged from the cell as illustratedin FIG. 1. Approximately half of the sodium chloride is converted tosodium hydroxide and chlorine in the process.

The effect of diaphragm structure on the performance of a chlor-alkalicell is quite complex. The diaphragm can be described in terms of poresize distribution, porosity, tortuosity, thickness and resultantpermeability of the structure. For a given set of cell operatingconditions, these parameters, and especially their uniformity across theactive area of the diaphragm, determine the electrical energy usage ofthe cell. Lack of uniformity of flow rates across the surface of thediaphragm cause areas of low brine velocity, which allows hydroxyl ionback migration, leading to poor current efficiency. This effect can beameliorated by using a thicker, less porous or more tortuous structure,leading however, to higher operating voltage and greater electricalenergy usage. The art in designing a diaphragm for chlor-alkaliproduction is to properly balance the diaphragm properties to minimizeoverall electrical energy usage by reducing operating voltage whilemaintaining high current efficiency. This is most effectively done witha diaphragm whose properties are highly uniform across its active area.

In the electrolysis of brine, the power consumption in terms of kilowatthour (kWh) per metric ton of sodium hydroxide can be expressed by thefollowing equation: ##EQU1##

Obviously it is economically desirable to achieve as high a causticcurrent efficiency as possible and require as low a voltage as possible.A desirable diaphragm will have a low "k" factor, k being the slope ofthe voltage versus current density relationship. Many commercialdiaphragm chlor-alkali cells operate at a maximum current density ofeither 2.3 kilo-amperes per square meter or 2.8 kilo-amperes per squaremeter.

A commonly used porous diaphragm is prepared from asbestos fiber byessentially a paper making process. Asbestos flock is slurried anddeposited in place on a screen in the electrolyzer to form a relativelythick, stiff diaphragm which is held together by the hydroxide gelsformed in the asbestos while in operation. The asbestos diaphragm hasoften been termed a "living diaphragm" in that it is constantly beingchanged by dissolution, erosion, redeposition and precipitation ofsilica and alkali earth hydroxides. Suspended particles and dissolvedalkali earth metals redeposit preferentially in the higher flow regionsallowing a leveling effect on permeability.

However, this "living" or reactive feature of the asbestos diaphragm cancontribute to a relatively short life. Usually, within 6-12 months,sufficient chemicals are leached out of the asbestos and the uniformityand porosity are so degraded that current efficiency drops tounacceptable levels. For the same reason, electrical upsets orfluctuations in the system can result in a very rapid destruction of theasbestos diaphragm. Finally, the asbestos diaphragm has a relativelyhigh k factor of about 0.55 volt square meter per kiloampere (Vm² /kA)such that, for example, at 2.8 kA/m², the diaphragm typically requires3.84 volts or more for operation, resulting in substantial power costs.For these reasons, the industry has sought more inert, more stablediaphragms, which can operate consistently at high current efficiencyand at lower voltage and which will not be destroyed by power upsets,fluctuations or outages.

A number of modified asbestos diaphragms have been developed. U.S. Pat.No. 3,853,720 discloses a preparation of a diaphragm for chlor-alkaliservice involving asbestos fiber, a second fibrous material includingpolytetrafluoroethylene (PTFE) fiber, and an organic exchange resin.U.S. Pat. Nos. 4,170,537, 4,170,538 and U.S. Pat. No. 4,170,539 describea diaphragm of an asbestos or polymer matrix containing inorganiczirconium or magnesium compounds and, in some cases, "Nafion® 601polymer solution", a colloidal dispersion of hydrolyzedperfluorosulfonic acid polymer, which is used to impregnate thestructure. All of these structures rely, to some extent, on the asbestosor the added compounds which generate hydroxide gels to regulateporosity and uniformity. Accordingly, though somewhat more stable thanunmodified asbestos, they suffer from the same deficiencies describedfor the asbestos diaphragm described above. These patents also mentionexpanded PTFE (EPTFE) as a possible polymer matrix but the pore sizerange specified, 0.8-50 microns, preferably 5-20 microns, is relativelylarge so that the permeability level is controlled by the hydroxide gelsformed within the diaphragm.

A number of U.S. Patents, U.S. Pat. Nos. 3,930,979, 4,113,912,4,224,130, 4,606,805, 4,385,150, 4,666,573, 4,680,101, 4,720,334 and4,341,614, describe porous PTFE diaphragms made wettable by variousmeans. U.S. Pat. Nos. 3,930,979, 4,250,002, 4,113,912, 4,385,150 and4,341,614, describe porous PTFE diaphragms prepared by combining PTFEpowder or fiber with a sacrificial filler. The mixture is formed into asheet and the filler is removed by dissolving it or decomposing it withheat thus leaving the PTFE sheet porous. The homogeneity of the mixtureand the particle size distributions of the filler and PTFE severelylimit the uniformity possible in the finished diaphragm. Because a largepercentage of the structure is removed to provide the necessaryporosity, the finished diaphragm is inherently weak. To offset theseuniformity and strength problems, the finished diaphragm must be verythick resulting in high operating voltage. A number of patents,including U.S. Pat. Nos. 4,606,805, 4,666,573, 4,113,912, 4,680,101 andU.S. Pat. No. 4,720,334, describe porous PTFE diaphragms prepared by aPTFE fiber slurry deposition process. The size, shape and sizedistribution of the PTFE fiber available leads to a large pore,inherently weak, non-uniform structure which must be made very thick toprovide utility. This trade-off results in high operating voltages. Inaddition, in U.S. Pat. Nos. 3,930,979, 4,113,912, 4,224,130, 4,250,002,4,341,614 and 4,606,805, no perfluoro ion exchange polymer is involvedso that an adequate level of hydrophilicity, which remains chemicallystable in a hostile environment such as a chlor-alkali cell, is notachieved. When an adequate level of hydrophilicity is not maintained,gas bubbles generated at the cathode will accumulate in the diaphragmpores blocking both bulk and ion flow. This reduces the effectivediaphragm area leading to an increase in operating voltage andeventually causing system shutdown. This is called "gas locking".

U.S. Pat. No. 3,944,477 describes a diaphragm of porouspolytetrafluoroethylene sheet material with a microstructurecharacterized by nodes and fibrils and having a multilayer structurewherein a number of such films are bonded together. Initial wettabilityis achieved by treatment with acetone and water, with no mention made oforganic surfactants. More importantly, there is no disclosure ofimpregnation with a perfluoro ion exchange polymer. While the diaphragmsof the present invention have given satisfactory performance after asmuch as 421 days, the reference reports no extended runs.

U.S. Pat. Nos. 4,089,758 and 4,713,163 describe porous diaphragmsinvolving EPTFE structures made hydrophilic with inorganic fillerparticles or organic surfactants. These diaphragms are susceptible togas locking, which will block ion and bulk fluid flow, resulting inincreasing operating voltage, decreasing current efficiency and ultimatesystem shutdown.

U.S. Pat. No. 3,940,916 describes a porous diaphragm made from a fabricspun from an ion exchange polymer. The pore size of this structure istoo large for efficient operation in a chlor-alkali cell. Because ofthis, very thick structures are required for high current efficiencyoperation resulting in high voltage.

U.S. Pat. No. 4,385,150 discloses, but does not claim, a porous asbestosor PTFE substrate impregnated with an organic solution of a fluorinatedcopolymer having a carboxyl functional group. The disclosure does notspecify the PTFE as having a microstructure characterized by a series ofnodes interconnected by fibrils, nor does it specify a multilayerconstruction. Accordingly, this PTFE structure does not provide theuniformity of structure, porosity and permeability necessary forsustained high efficiency operation in a chlor-alkali cell.

U.S. Pat. Nos. 3,692,569, 4,453,991, 4,865,925 and 4,348,310 andJapanese Patent Applications JPA-61-246,394 and JPA-63-99,246 describeand claim porous diaphragms involving EPTFE coated with perfluoro ionexchange resin for use in electrochemical cells. However, the EPTFEcited is not a layered structure and will not, at a correspondingthickness, provide the small pore size and uniformity of structurenecessary for efficient operation of a chlor-alkali cell, especially inthicknesses exceeding 20 mils. Moreover, U.S. Pat. Nos. 4,453,991 and4,348,310 specify impregnation of the EPTFE with perfluoro ionomersolutions with equivalent weights exceeding 1000. The relatively largemicelles of these high equivalent weight systems cannot penetrate arelatively thick, small pored EPTFE structure to uniformly andthoroughly impart sufficient hydrophilicity to the entire structure toallow efficient chlor-alkali diaphragm operation.

U.S. Pat. No. 4,865,925 discloses use of an EPTFE/perfluoro ion exchangeresin structure for a fuel cell, which is an electrochemical cell, butthe structure would not be suitable for a diaphragm because it is porousto gas. A chlor-alkali cell requires that hydrogen from the cathode sidemust not mix with chlorine from the anode side because mosthydrogen/chlorine mixtures are explosive. The reference makes nodisclosure of the need for thorough impregnation, the need for at leastfour layers of EPTFE thermally bonded together, or the preference forcertain equivalent weights for the ion exchange resin.

U.S. Pat. No. 4,277,429 describes a method for producing a porous PTFEthat is asymmetric in the sense that there is a measurable difference inbubble point between one surface and the reverse side surface. Slightlydifferent permeability to isopropanol is noted in one direction than inthe reverse direction. Such a structure, however, is monolithic and notlayered and would not provide the high level of uniformity of pore sizeand pore size distribution necessary for efficient operation of achlor-alkali cell. In addition, the interior and exterior surfaces ofthis porous PTFE are hydrophobic and would "gas lock" in chlor-alkaliproduction or in other electrolytic or filtration uses where gasentrainment is a potential problem.

International Patent Application No. PCT/US88/00237, publication numberWO88/05687 and its counterpart U.S. Pat. No. 4,863,604, describes amicroporous, asymmetric, integral, composite polyfluorocarbon membraneof two or more sheets of microporous fluorocarbon polymer havingdifferent average pore sizes. These structures, however, would not beuseful as diaphragms in a chlor-alkali cell. Such sheets are not EPTFEstructures but rather are prepared by incorporating a particulate,inorganic, solid, pore forming filler, removeable by leaching andheating, into the polytetrafluoroethylene polymer, and shaping theresultant mixture by preforming and calendering it into aself-sustaining sheet or film. The multilayer structure is assembled bystarting with a sheet of PTFE/pore forming filler which has small poreforming filler particles. On top of this sheet are layered additionalsheets of PTFE/pore forming filler which contain progressively largerpore forming filler particles. The sheets are bonded with heat andpressure, followed by sintering. Finally, the pore forming filler isremoved by leaching or heat, thus leaving the multilayer PTFE sheetporous. As discussed above, the homogeneity of the mixture and theparticle size distributions of the filler and PTFE severely limit theuniformity possible in microporous structures prepared by leaching orotherwise removing incorporated particles. This limitation is furthercompounded by the limitation on sharply fractionating particle sizes forthe various layers of the asymmetric structure. Also, as mentionedabove, because a large percentage of the structure is removed to providethe necessary porosity, the finished structure is inherently weak. Todeal with these uniformity and strength problems, the finished diaphragmmust be very thick, which is undesirable in electrolytic operationsbecause of the high operating voltage required. In addition, inPCT/US88/00237 (WO88/05687) and in U.S. Pat. No. 4,863,604, no perfluoroion exchange polymer is involved so that an adequate level ofhydrophilicity which remains stable in a hostile environment is notachieved. As discussed above, when an adequate level of hydrophilicityis not maintained, "gas locking" occurs reducing effective diaphragmarea leading to an increase in operating voltage.

U.S. Pat. No. 4,385,093 describes a porous PTFE article prepared bylayering together PTFE components followed by expanding in one or moredirections. The resulting article has very high interlayer bondstrengths and appears uninterrupted at the layer interfaces. Theinterlayer bond strength of this article was shown to be much higherthan a composite prepared by layering and sintering two already expandedPTFE sheets. The high interlayer bond strength is desirable in certainapplications to prevent delamination of the layers due to gas, liquid orosmotic pressure which may build up inside the structure during use. Themethod of U.S. Pat. No. 4,385,093 does not take advantage of theaveraging effect of layering because the expansion is carried out afterthe layering step. The resulting product is less uniform in structureand pore size than the article of this invention which is made bylayering already expanded sheets. Further, the pure PTFE structure ofU.S. Pat. No. 4,385,093 has an inherent tendency to entrain gas incertain aqueous, electrolytic or filtration applications and willeventually gas lock.

U.S. Pat. No. 4,341,615 and U.S. Pat. No. 4,410,638 both claim awettable, microporous diaphragm for electrolysis having a base offluorinated resin, the pores of the microporous diaphragm havingdeposited therein a copolymer of an unsaturated carboxylic acid and anon-ionic unsaturated monomer. The structure is monolithic and notlayered and does not provide the uniformity of structure necessary toprovide high current efficiency and low operating voltage forchlor-alkali operation. This deficiency is further compounded in thatthis monolithic, fluorinated resin construction is prepared by leachingout calcium carbonate particulates from the fluorinated resin composite.Accordingly, as pointed out earlier, the homogeneity of the mixture andparticle size distribution of the filler and resin severely limit theuniformity of structure possible in the microporous sheet. The copolymerdeposited within the pores to impart hydrophilicity is notperfluorinated and does not provide the necessary durability in thecorrosive environment of chlor-alkali service.

The present invention is a porous, multilayer construction comprisingmultiple layers of porous EPTFE bonded together wherein the internal andexternal surfaces are at least partially coated with a perfluoro ionexchange polymer. Two U.S. patent applications, U.S. Ser. No. 206,884and U.S. Ser. No. 278,224 now U.S. Pat. No. 4,902,308 and U.S. Pat. No.4,954,388 in the names of some of the inventors of the presentinvention, involve the same starting materials.

U.S. Ser. No. 206,884, "Composite Membrane" discloses a thin porousexpanded PTFE whose internal and external surfaces are coated with ametal salt of a perfluoro ion exchange polymer. That composite is porouslike the present invention but, in contrast to the present invention, itis much thinner. In that application, the perfluoro ion exchange polymerserves as an anchor for active metal ions which may scavenge, catalyzeor otherwise react with fluids passing through the porous structure. TheEPTFE component is a single layer construction, not the multilayer formof the present invention.

U.S. Ser. No. 278,224 is a multilayer composite comprising a reinforcingfabric bonded to an expanded PTFE film which is laminated to acontinuous film of perfluoro ion exchange polymer. In contrast to thepresent invention, that construction is a non-porous composite where theEPTFE is used as an interlayer between the continuous film of perfluoroion exchange polymer and a reinforcing fabric. In addition, the EPTFEcomponent is a single layer, not the multilayer construction of thepresent invention.

The carboxylic polymers with which the present invention is concernedhave a fluorocarbon backbone chain to which are attached the functionalgroups or pendant side chains which in turn carry the functional groups.When the polymer is in melt-fabricable form, the pendant side chains cancontain, for example, ##STR1## groups wherein Z is F or CF₃, t is 1 to12, and W is --COOR or --CN, wherein R is lower alkyl. Preferably, thefunctional group in the side chains of the polymer will be present interminal ##STR2## groups wherein t is 1 to 3.

The term "fluorinated polymer", used herein for carboxylic and forsulfonic polymers, means a polymer in which, after loss of any R groupby hydrolysis to ion exchange form, the number of F atoms is at least90% of the total number of F, H and Cl atoms in the polymer. Forchloralkali cells, perfluorinated polymers are preferred, though the Rin any COOR group need not be fluorinated because it is lost duringhydrolysis.

Polymers containing ##STR3## side chains, in which m is 0, 1, 2, 3 or 4,are disclosed in U.S. Pat. No. 3,852,326.

Polymers containing --(CF₂)_(p) COOR side chains, where p is 1 to 18,are disclosed in U.S. Pat. No. 3,506,635.

Polymers containing ##STR4## side chains, where Z and R have the meaningdefined above and m is 0, 1, or 2 (preferably 1) are disclosed in U.S.Pat. No. 4,267,364.

Polymers containing terminal --O(CF₂)_(v) W groups, where W is definedabove and v is from 2 to 12, are preferred. They are disclosed in U.S.Pat. Nos. 3,641,104, 4,178,218, 4,116,888, British Patent Nos.2,053,902, EP No. 41737 and British Patent No. 1,518,387. These groupsmay be part of ##STR5## side chains, where Y=F, CF₃ or CF₂ Cl.Especially preferred are polymers containing such side chains where v is2, which are described in U.S. Pat. Nos. 4,138,426 and 4,487,668, andwhere v is 3, which are described in U.S. Pat. No. 4,065,366. Amongthese polymers, those with m=1 and Y=CF₃ are most preferred.

The above references describe how to make these polymers.

The sulfonyl polymers with which the present invention is concerned arefluorinated polymers with side chains containing the group ##STR6##wherein R_(f) is F, Cl, CF₂ Cl or a C₁ to C₁₀ perfluoroalkyl radical,and X is F or Cl, preferably F. Ordinarily, the side chains will contain--OCF₂ CF₂ CF₂ SO₂ X or --OCF₂ CF₂ SO₂ F groups, preferably the latter.For use in chloralkali membranes, perfluorinated polymers are preferred.

Polymers containing the side chain ##STR7## where k is 0 or 1 and j is3, 4, or 5, may be used. These are described in British Patent No.2,053,902.

Polymers containing the side chain --CF₂ CF₂ SO₂ X are described in U.S.Pat. No. 3,718,627.

Preferred polymers contain the side chain ##STR8## where R_(f), Y and Xare defined above and r is 1, 2, or 3, and are described in U.S. Pat.No. 3,282,875. Especially preferred are copolymers containing the sidechain ##STR9##

Polymerization can be carried out by the methods described in the abovereferences. Especially useful is solution polymerization using ClF₂CCFCl₂ solvent and (CF₃ CF₂ COO)₂ initiator. Polymerization can also becarried out by aqueous granular polymerization as in U.S. Pat. No.2,393,967, or aqueous dispersion polymerization as in U.S. Pat. No.2,559,752 followed by coagulation as in U.S. Pat. No. 2,593,583.

To make the lowest equivalent weight ion exchange polymers, copolymer inthe melt-fabricable (for example, --SO₂ F or --COOCH₃) form may beextracted as in U.S. Pat. No. 4,360,601 and the extracted polymerisolated for use in making the diaphragm. The extract has lowerequivalent weight than the starting material.

The copolymers used herein should be of high enough molecular weight toproduce films which are self-supporting in both the melt-fabricableprecursor form and in the hydrolyzed ion-exchanged form.

SUMMARY OF THE INVENTION

A multilayer, porous, composite, shaped article is provided comprisingmultiple layers of porous, expanded polytetrafluoroethylene bondedtogether, the composite, shaped article having at least a portion of itsexterior surfaces and at least a portion of its interior pore surfacescoated with a perfluoro ion exchange polymer. Preferably, the compositearticle has substantially all of its exterior surfaces and substantiallyall of its interior pore surfaces coated with a perfluoro ion exchangepolymer. The composite article may contain a water soluble surfactantwithin its pores. The article may be in the form of a sheet or a tube.The perfluoro ion exchange polymer is a perfluorosulfonic acid polymerof equivalent weight less than 1000, a perfluorocarboxylic acid polymerof equivalent weight less than 1000, a mixture of perfluorosulfonic acidpolymer and perfluorocarboxylic acid polymer of equivalent weight lessthan 1000, or a copolymer containing perfluorosulfonic acid andperfluorocarboxylic acid groups, with an equivalent weight less than1000. The percentage by weight of perfluoro ion exchange polymer in thecomposite exceeds 2%. The sheets are relatively thick, having athickness exceeding 0.25 millimeters, preferably between about 0.76millimeters and about 5.0 millimeters. The composite article has apermeability to water containing 0.1% tetra ethyl ammoniumperfluorooctane sulfonate between about 0.01 and about 3.0 reciprocalhours at 23° C. under a 20 cm head of water and a specific gravitybetween about 0.05 and about 1.1, preferably between about 0.15 andabout 0.7. The composite article may have an asymmetric fine structure,wherein at least two of the layers have different microporousstructures. The two or more layers may have methanol bubble point valueswhich differ by at least 10% or have specific gravities which differ byat least 5%.

In an electrolytic cell containing anode and cathode compartmentsseparated by a diaphragm, an improved diaphragm is provided comprising amultilayer, porous composite diaphragm of multiple layers of porous,expanded polytetrafluoroethylene bonded together, the compositediaphragm having at least a portion of its exterior surfaces and atleast a portion of its interior pore surfaces coated with a perfluoroion exchange polymer. A plurality of composite diaphragms may be used toseparate a plurality of cell compartments of an electrolytic cell. Thecomposite diaphragm preferably has substantially all of its exteriorsurfaces and substantially all of its interior pore surfaces coated witha perfluoro ion exchange polymer. The diaphragm may initially containwater soluble surfactant within its pores to enhance initial wetting.The diaphragm may have an asymmetric fine structure, wherein at leasttwo of the multiple layers have different microporous structures,wherein the two or more layers have specific gravities which differ byat least 5%. The asymmetric diaphragm preferably is oriented such that,in the two or more layers, the layer of lower specific gravity is closerto the anode side of the cell and the layer of higher specific gravityis closer to the cathode side of the cell.

The multilayer EPTFE structure of this invention yields an exceptionallevel of uniformity in diaphragms such that they operate at cellvoltages and current efficiencies significantly better than those ofprior art. The perfluoro ion exchange coating on the interior andexterior surfaces of the diaphragm, the other essential feature of thisinvention, provides a level of hydrophilicity that prevents gas lockingand leads to sustained operation at high current efficiency and lowvoltage.

An improved filter medium is also provided comprising a multilayer,porous, composite, shaped article of multiple layers of porous, expandedpolytetrafluoroethylene bonded together, the composite having at least aportion of its exterior surfaces and at least a portion of its interiorpore surfaces coated with a perfluoro ion exchange polymer. The filtermedium may be in the form of a sheet or a tube.

Another aspect of the present invention is a process for coating theexterior surfaces and at least a portion of its interior pore surfaceswith a perfluoro ion exchange polymer. One feature of this process isthe incorporation in the liquid coating composition of an organiccompound which enables the composition to fully wet a horizontal surfaceof nonporous PTFE (as distinguished from expanded PTFE) and to remainspread out as the composition dries instead of forming droplets. Anotherfeature of the present invention is the use of vacuum to remove most ofthe air from the EPTFE before the coating composition is introduced fromone side of the EPTFE.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of an electrochemical cell.

FIG. 2 is a photomicrograph taken at 45× magnification of thecross-section of a symmetric composite according to the invention.

FIG. 3 is a photomicrograph taken at 5000× magnification of thesymmetric composite and shows the microstructure of nodes and fibrilscoated with a perfluoro ion exchange resin.

FIG. 4 is a photomicrograph take at 50× magnification of thecross-section of an asymmetric composite according to the invention.

FIG. 5 is a photomicrograph taken at 5000× magnification of theasymmetric composite and shows the microstructure of nodes and fibrilscoated with a perfluoro ion exchange resin.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS WITHREFERENCE TO THE DRAWINGS

A composite, porous, liquid-permeable article is provided which is amultilayer structure of discrete, bonded layers of porous, expandedpolytetrafluoroethylene (EPTFE). The composite has its interior andexterior surfaces coated with a perfluoro ion exchange polymer to renderthe composite hydrophilic so as to resist gas locking in aqueous media.Initially, the diaphragm may also contain a water soluble surfactant toassist in initial water penetration into the pores of the composite. Animproved electrolytic cell is provided having the composite diaphragm asthe porous separator in electrolysis processes, particularlyelectrolysis of alkali halide solutions. The diaphragm is also useful asan improved filter medium.

More specifically, a mechanically strong, porous, composite,liquid-permeable diaphragm is provided which is a multilayer structureof discrete bonded EPTFE layers. This relatively thick, preferablygreater than 5 mil thick, layered structure provides a small pore sizeand uniformity of structure not attainable in monolithic EPTFEstructures. By coating the interior and exterior surfaces of thisstructure with a perfluoro ion exchange resin of equivalent weight lessthan 1000, hydrophilicity of the resulting composite can be greatlyincreased, thereby drastically reducing the composite's tendency toentrain gas in the pores. Initial wetting is assured by initiallyincorporating a water soluble surfactant in the pores when desirable.

In the electrolysis of brine, the porous composite of this inventionprovides a chemically stable, porous diaphragm with a uniformmicrostructure such that uniformity of flow and high current efficiencycan be obtained without the reactive hydroxide gel deposits encounteredwith conventional diaphragms. Further, the porous composite of thisinvention can withstand numerous electrical upsets, shutdowns orfluctuations encountered in normal cell room operations withoutsignificant loss of performance. The porous multilayer composite of thisinvention also provides a small pore size and uniformity of structureand flow not obtainable in the thick, monolithic EPTFE structures or inthe PTFE structures prepared by slurry deposition of fibers or byleaching soluble particulates from a filled PTFE sheet.

The perfluoro ion exchange polymer is a copolymer of tetrafluoroethylenewith one of the functional comonomers disclosed herein. The ratio oftetrafluoroethylene to functional comonomer on a mole basis is 1.5 to5.6:1. For each comonomer, the most preferred ratio oftetrafluoroethylene to functional comonomer is determined by experiment.

Through the use of liquid compositions of perfluoro ion exchange resinof equivalent weight less than 1,000 and by virtue of the much smallermicelle dimensions of these dispersions as compared to dispersions fromperfluoro ion exchange resins with equivalent weight exceeding 1,000,the very small pores of the relatively thick multilayered structures ofthis invention can be penetrated and the exterior surfaces and interiorpore surfaces can be uniformly coated with perfluoro ion exchange resin.A water soluble surfactant can also be introduced to facilitate initialwetting by aqueous media. For best performance, any surfactant presentmust be washed away before electrolysis is started. The perfluoro ionexchange resin, however, will not wash away nor will it be chemicallydegraded by the corrosive liquors of a chlor-alkali cell. It remains,coating the pores, and imparting a level of hydrophilicity such that gasgenerated in the electrolytic process will not displace electrolyte inthe pores of the diaphragm. This remedies a deficiency of porous PTFEdiaphragms of prior art where dewet or "gas locked" areas with blockedelectrolyte flow often cause voltage rise and ultimate shutdown. Theporous PTFE diaphragms of the prior art do not involve a chemicallyinert polymer to impart hydrophilicity or, if they do, they employ ahigher equivalent weight polymer which, because of micelle size, cannotpenetrate to uniformly coat the interior surfaces of very small pores inthe multilayer EPTFE composite of this invention.

It has been found that a representative k factor obtained with theporous composite of this invention is about 0.32 Vm² /kA. This resultsin considerable power savings over the 0.55 Vm² /kA k factor of asbestosor the 0.48 Vm² /kA k factor of modified asbestos diaphragms in currentuse.

By the layered approach, with proper selection of the EPTFE componentlayers, coupled with coating the interior and exterior surfaces of themultilayered article with a perfluoro ion exchange resin, an asymmetricstructure that will operate well as an electrolytic separator orfiltration medium can be created.

As used in this application, the term "asymmetric structure" means amultilayered, composite structure in which at least two of the multiplelayers have different microporous structures, i.e., at least two of thelayers in the composite have specific gravities which differ by at least5%.

Such an asymmetric structure has utility as a diaphragm in achlor-alkali cell. The preferred method of use is to orient thediaphragm such that the larger pore size, as indicated by a lowermethanol bubble point (ASTM F316-80), faces the anode compartment. Inthis mode, a higher current efficiency is achieved. This is probablybecause the linear velocity of the electrolyte, in the direction of thecathode, increases as the electrolyte moves through the diaphragm andits effect on counteracting the back migration of the hydroxyl ion iscorrespondingly enhanced.

A detailed description of the invention and preferred embodiments isbest provided with reference to the drawings and the examples whichfollow.

FIG. 1 is a schematic diagram of a chlor-alkali cell 8 containing anode14 and cathode 16 in operation. A multilayered composite according tothe invention and useful as the diaphragm 10 in such a cell is shown.FIG. 2 is a photomicrograph taken at 45× magnification of across-section taken in the thickness or Z-direction through themultilayered sheet 10. The individual layers 12 which make up sheet 10are discernible. FIG. 3 is a photomicrograph taken at 5000×magnification of the sheet 10 shown in FIG. 2. Therein themicrostructure of nodes and fibrils coated with a perfluoro ion exchangeresin is shown.

FIGS. 4 and 5 are photomicrographs taken at 50× and 5000×, respectively,of an asymmetric sheet according to the invention. The overall sheet 20is seen in FIG. 4 to be made up of thick layers 22 and relativelythinner layers 24. Layers 24 have a lower specific gravity than layers22. The coated microstructure of this composite is shown in FIG. 5 whichwas taken at 5000× magnification.

The examples which follow are intended to be illustrative of theinvention but not limitative in any way.

Attempts to duplicate the 95-95% current efficiency experiments weresuccessful, but in some cases wherein membrane thickness was less than90 mils, they gave a current efficiency as much as 4% lower.

In general, in order to make the composite articles of the invention,expanded PTFE sheeting having a microstructure characterized by a seriesof nodes interconnected by fibrils and having a Gurley air flow of 0.8sec. to 27 sec., thickness between 0.2 mil and 10 mil, methanol bubblepoint (ASTM F316-80) between 0.7 psi and 40 psi, is wound around acylindrical mandrel.

The EPTFE sheet suitably has a thickness of 25-125 micrometers, or1.0-5.0 mils.

The length and diameter of the mandrel can be varied to give the desireddimensions for the finished sheet. Multiple layers, greater than 4, arewound onto the mandrel and the number of layers is varied to give thedesired thickness and uniformity. The membrane is restrained at the endsof the mandrel by mechanical clamps or bands.

The layers of EPTFE sheeting are bonded together by immersion in amolten salt bath at a temperature above the cystalline melt point ofEPTFE. The layered EPTFE composite is allowed to cool slowly on themandrel in air. The layered composite is cut and removed from themandrel to yield a flat sheet.

Impregnation of the layered flat sheet is carried out by using analcohol based liquid composition of perfluorosulfonic acid ion exchangepolymer. Polymer solids loading in the liquid composition can range from0.5% up to 10%. Up to 8% surfactant or surfactant blend can be includedto aid in distribution of the ion exchange polymer and in initial waterwetting of the finished product. The layered flat sheet is fully wetwith impregnating liquid composition. The impregnant is introduced fromone side so as to avoid trapping air inside the structure.

Another feature of the preferred coating process is to evacuate most ofthe air from the EPTFE before the liquid composition is added to justone surface of the EPTFE. A suitable vacuum is an absolute pressure of125 mm Hg, but the absolute pressure is not critical. It is believedthat this feature means that the liquid composition moves in just onedirection through the EPTFE and it encounters less air which could formair bubbles during the coating process and thus prevent coating of localareas of the EPTFE.

The liquid composition used to coat the exterior surfaces and at least aportion of its interior pore surfaces with a perfluoro ion exchangepolymer preferably contains an organic compound or compounds that enablethe composition to fully wet the surface of a full density EPTFE uponwhich it is poured. The compound shall be soluble in water andcompatible with the solvents used in the liquid composition. Thecompound shall wet EPTFE and the perfluoro ion exchange polymer, andshall have a boiling point above the boiling point of water but belowthe decomposition temperature of the perfluoro ion exchange polymer.This combination of properties enables the liquid composition to spreadevenly and uniformly over the external surfaces and internal poresurfaces of the EPTFE and to dry without drawing up into discretedroplets which would contribute to non-uniform coating of the EPTFE withion exchange resin. A suitable organic compound is 1-methoxy-2-propanol.

Excess impregnating liquid is removed from the outside of the sheetingby wiping or squeegeeing. The wet sheet is then restrained at its edgesto prevent shrinkage as the sheet is dried.

Drying can be carried out in air at temperatures ranging from 15° C. to120° C. The preferred drying conditions are in air at 23° C. A postdrying bake can be carried out at temperatures between 30° C. and 150°C.

EXAMPLE 1

Two relatively thick multilayer EPTFE composites were prepared bydifferent methods. The first was prepared by layering nine full density,extruded PTFE tapes and biaxially expanding and sintering this compositeaccording was to the disclosure of U.S. Pat. No. 4,187,390. The secondcomposite was prepared by winding multiple layers of biaxially expanded,sintered PTFE sheeting onto a 31/2 inch diameter aluminum mandrel andsintering these layers together by immersion in a molten salt solutionfor one minute at 370° C. The first sample will be referred to as"layered before expansion composite" and the second will be referred toas "layered after expansion composite", the latter being the precursorof the composite of this invention.

Specimens were cut from both of these composites and a specimen was cutfrom the single biaxially expanded sheet which was used to make thelayered after expansion composite. Specimen size was chosen for eachtype of sheeting to give approximately the same total weight perspecimen. The biaxially expanded PTFE sheeting specimens were cut so asto produce 12"×12" squares, the layered before expansion compositespecimens were cut to yield 41/2"×41/2" squares and the layered afterexpansion specimens were cut to yield 31/4"×31/4" squares. A group ofsix specimens was taken from at least two different areas of the bulksheet of each sample type to illustrate across-the-web variation.

Testing was carried out to determine the uniformity of each type ofsheeting with respect to a number of physical characteristics. Eachspecimen was weighed to ±0.002 g accuracy, thickness was measured with asnap gauge, and air flow permeability was measured using a GurleyDensometer according to ASTM D726-58. Thickness and air flowmeasurements were taken in at least four areas of each specimen. Densityvalues were calculated from weight and thickness data. Results of thistesting can be seen in Table 1.

Range is defined as the difference between the high and low individualvalues for a set of data. The percent range is the range value dividedby the average and is a measure of the full scope of values normalizedto an average value of one. Similarly, percent standard deviation is thestandard deviation for a set of data divided by the average and is ameasure of the scatter of data normalized to an average value of one.These values are normalized measures of uniformity for a given physicalproperty.

Normalizing the range and standard deviation values enables a comparisonof the levels of uniformity of the different films with respect to eachphysical property examined.

Referring to Table 1, percent range and percent standard deviationvalues for the layered after expansion composite were lower than thelayered before expansion composite and the biaxially expanded singlelayer film in thickness, density and air flow measurements. Thisdemonstrates that the technique of layering an expanded PTFE sheet toform a thick composite, surprisingly and unexpectedly, gives a much moreuniform structure than a thick sheet prepared by layering full densityPTFE tapes and then expanding. The data above demonstrates that bylayering expanded PTFE sheeting, variations in the sheet are averaged,giving a much more uniform layered composite than the original singlelayered sheet.

                  TABLE 1                                                         ______________________________________                                                 Biaxially                                                                             Layered Before                                                                            Layered After                                             Expanded                                                                              Expansion   Expansion                                                 PTFE    Composite   Composite                                        ______________________________________                                        Thickness  3.53      39.3        69.7                                         Average                                                                       High       4.05      47.0        72.5                                         Low        3.00      23.0        66.7                                         Std. Dev.  0.223     4.65        1.91                                         Std. Dev. %                                                                              6.3       11.8        2.7                                          Range      1.05      24.0        5.8                                          Range %    29.7      61.1        8.3                                          Density Average                                                                          0.290     0.264       0.302                                        High       0.308     0.293       0.309                                        Low        0.275     0.248       0.294                                        Std. Dev.  0.010     0.011       0.005                                        Std. Dev. %                                                                              3.3       4.3         1.5                                          Range      0.033     0.045       0.015                                        Range %    11.4      17.0        5.0                                          Gurley Air Flow                                                                          9.7       68.8        94.6                                         Average                                                                       High       12.3      82.6        97.5                                         Low        7.5       56.2        90.4                                         Std. Dev.  1.1       5.6         1.9                                          Std. Dev. %                                                                              11.2      8.1         2.0                                          Range      4.7       26.4        7.1                                          Range %    48.9      38.4        7.5                                          ______________________________________                                    

EXAMPLE 2

A section of expanded PTFE sheeting having an average methanol bubblepoint of 11.8 psi (ASTM F316-80), an air flow of approximately 5.1seconds as measured by Gurley Densometer (ASTM D726-58) and thickness ofapproximately 4.4 mil was wound onto an aluminum mandrel (3.5" o.d. and9" in length). A total of twenty (20) layers of EPTFE sheeting werewound onto the mandrel. This sheeting was restrained by placing hoseclamps around the circumference of the mandrel at each end. The layersof EPTFE sheet were bound together by immersing the wound mandrel in amolten salt bath at 370° C. for one minute. The EPTFE wound mandrel wasthen allowed to cool slowly in room temperature air.

The layered EPTFE was cut along the length of the mandrel and removed toform a flat sheet. A section of this layered EPTFE sheet was impregnatedwith a liquid composition comprising 3.2% perfluorosulfonic acid polymer(equivalent weight 920 to 950) derived from a precursor copolymer oftetrafluoroethylene and ##STR10## 1.2% Triton X-100 non-ionic surfactant(Rohm and Haas) and 0.4% Triton CF-54 non-ionic surfactant (Rohm andHaas) in ethyl alcohol. The wet layered EPTFE structure was restrainedto prevent shrinkage and was allowed to dry at approximately 23° C.overnight.

The resulting composite diaphragm contained 9.0% perfluoro sulfonic acidpolymer by weight.

The EPTFE/perfluoro ion exchange polymer composite was wet with a 0.1%tetraethylammonium perfluorooctane sulfonate solution in water tofacilitate start up.

The sample described above was tested in a laboratory scale cellconsisting of a glass anode compartment separated from an acryliccathode compartment by the diaphragm. The diaphragm was sealed in placeusing EPDM gaskets. The anode compartment consisted of an anolytechamber containing about 500 milliliters of anolyte, a DSA® anodeobtained from Oxytech, Inc., a cell heater for temperature control, abrine feed line and a vertical tube connected to a chlorine outlet. Thistube allowed disengagement of the chlorine and allowed an anolyte headof up to about 80 cm to be formed before overflow of the anolyteoccured. The cathode compartment included a heavy gauge mild steel wirescreen (of a type used in commercial diaphragm cells) tack-welded to amild steel current distributor, a hydrogen disengagement area and acatholyte discharge. The cell had an active diaphragm area of 45 squarecentimeters, was controlled at a temperature of about 85° C., and wasoperated at a current of 11.25 amperes, resulting in a current densityof 2.5 kiloamperes/square meter or 232 amperes/square foot.

Cell voltages were measured between points near the entrances of theelectrodes into the cell bodies, and current efficiencies werecalculated from the ratio of caustic produced over a sixteen hour period(from the total sample weight and titration to determine causticconcentration) to the number of coulombs supplied to the cell duringthis time. Electrical energy consumption of the cell is reported inkilowatt-hours per metric ton of caustic produced, which is calculatedfrom the cell voltage and caustic current efficiency (CE) by thefollowing equation:

    Electrical Energy Consumption=67010× (cell voltage)/(CE)

in which the cell voltage is in volts and caustic current efficiency(CE) in percentage rather than fractional units. Another importantparameter reported is k factor, which is the slope of the cell voltageversus the current density at current densities greater than onekiloampere per square meter. This normalizes data taken at differentcurrent densities, because voltage is linear with current density forall practical current densities above one kiloampere per square meter.For simplicity, the k factor was estimated by the following correlation:

    k factor=(cell voltage-2.3 volts)/(current density)

in which the cell voltage is measured in volts and the current densityin kiloamperes per square meter. For samples operated at differentcurrent densities, the intercept was found to always be slightly greaterthan 2.3 volts, implying that this estimate of k factor gives an upperlimit to the true value of the slope.

Typical operating conditions include an exit caustic concentration ofapproximately 10% and salt conversion of 52-55%. Brine was fed into thecells at a rate that was controlled to produce nominally 10% (by weight)caustic in the catholyte. Two kinds of brine were used in the tests:membrane quality brine, in which calcium and magnesium levels were keptbelow 50 ppb total, and diaphragm quality brine, in which the totalcalcium and magnesium were maintained between 0.9 and 1.8 ppm. Thediaphragm quality brine came from two sources: spiking the membranequality brine with calcium and magnesium salts, and filtered brine froman operating asbestos diaphragm plant.

The sample diaphragm described above was installed in a laboratory cellwhile wet with the water/surfactant solution. Membrane quality brine wasallowed to flow through the diaphragm overnight without applied current.The sample was removed from the cell for several hours for cellmodifications, then replaced and the brine feed restored. After a totalof three days from the initial installation, a current of 11.25 ampereswas applied. For the first thirty days of operation, the average cellvoltage was 3.12 volts and caustic current efficiency was 95.4%, whilethe cell produced 10.0% caustic. Over the next thirty days of operation,the cell voltage averaged 3.07 volts and the current efficiency was95.8% at an average of 10.2% caustic production. For days 61 to 132, theaverage cell voltage was 3.14 volts and current efficiency was 95.6%while producing an average of 10.2% caustic. At this time, the cellcracked and the anolyte compartment drained. Less than one-third of thediaphragm remained in contact with the electrolytes. The diaphragm wasremoved, placed in a mixture of brine and surfactant, then installed ina new cell after about a one-week delay. The diaphragm was operated inthe new cell for an additional 60 days with an average cell voltage of3.18 volts, an average current efficiency of 95.7% and an averagecaustic concentration of 10.1%. These data are summarized with powerconsumptions and k factors in Table 2. After the cell hydraulicsstabilized, the daily anolyte head measurements averaged 23 centimeterswith a standard deviation of 3.3 centimeters.

                  TABLE 2                                                         ______________________________________                                               Caustic          Cell  kWh/    k factor                                Days   wt. %    CE %    Volts MT NaOH V/(kA/m.sup.2)                          ______________________________________                                         0-30  10.0     95.4    3.12  2190    0.33                                    31-60  10.2     95.8    3.07  2150    0.31                                     61-132                                                                              10.2     95.6    3.14  2200    0.34                                    142-201                                                                              10.1     95.7    3.18  2230    0.35                                    Avg.   10.1     95.6    3.13  2190    0.33                                    ______________________________________                                    

EXAMPLE 3 (COMPARATIVE)

A long section of expanded PTFE sheeting, the same as in Example 2, withan average methanol bubble point of 11.8 psi (ASTM F316-80), an air flowof approximately 5.1 second as measured by Gurley Densometer (ASTMD726-58) and thickness of approximately 4.4 mil was wound onto analuminum mandrel (31/2" o.d. and 9" in length). A total of 20 layers ofEPTFE sheeting were wound onto the mandrel. This sheeting was restrainedby placing hose clamps around the circumference of the mandrel at eachend. The layers of EPTFE sheeting were bonded together by immersing thewound mandrel in a molten salt bath at 370° C. for one minute. The EPTFEwound mandrel was then allowed to cool slowly in room temeprature air.

The layered EPTFE was cut along the length of the mandrel and removed toform a flat sheet. A section of this layered EPTFE sheet was wet withisopropyl alcohol and placed in a permeability testing apparatus. Thehigh head chamber of the cell was quickly filled with 0.1%tetraethylammonium perfluorooctane sulfonate in water and this solutionwas allowed to flow through the sample and displace the isopropylalcohol. After the sample was fully wet with solution, permeability wasmeasured.

The resulting diaphragm was 70 mils thick, had a Gurley air flow of 66sec. and a permeability of 0.412 reciprocal hours to 0.1%tetraethylammonium perfluorooctane sulfonate in water when measured at23° C. and at a 20 cm head height differential. This diaphragm samplecontained no perfluoro ion exchange polymer.

The diaphragm was installed in a laboratory cell while wet with thesurfactant/water solution and tested as described in Example 2. Membranequality brine was allowed to flow through the diaphragm overnightwithout applied current. The current was started and increased to 11.25ampere over a ten-minute period. The initial cell voltage at fullcurrent was 3.12 volts. After one day on load, the cell was producing10.0% caustic at 2.76 volts with a current efficiency of 86.5%. Aftertwo days, the cell was producing 11.0% caustic at 3.48 volts with acurrent efficiency of 94.0%. The cell voltage increased above theequipment limits (about 10-15 volts) over the next 8 hours, causing thecurrent to be interrupted. The cell could not be restarted withoutexceeding the equipment's voltage capacity.

EXAMPLE 4

A section of expanded PTFE sheeting with an average methanol bubblepoint of 11.8 psi (ASTM F316-80), an air flow of approximately 5.1seconds as measured by Gurley Densometer (ASTM D726-58) and thickness ofapproximately 4.4 mil was wound onto an aluminum mandrel (6" o.d. and 9"in length). A total of twenty layers of EPTFE sheeting were wound ontothe mandrel. This sheeting was restrained by placing hose clamps aroundthe circumference of the mandrel at each end. The layers of EPTFEsheeting were bonded together by immersing the wound mandrel in a moltensalt bath at 370° C. for one minute. The EPTFE wound mandrel was thenallowed to cool slowly in room temperature air.

The layered EPTFE was cut along the length of the mandrel and removed toform a flat sheet. A section of this layered EPTFE sheet was impregnatedwith a liquid composition comprising 3.2% perfluoro sulfonic acidpolymer (equivalent weight 920 to 950), as in Example 2, 1.2% TritonX-100 non-ionic surfactant (Rohm and Haas), 0.4% Triton CF-54 non-ionicsurfactant (Rohm and Haas) and 0.6% tetraethylammonium perfluorooctanesulfonate in ethyl alcohol. The wet layered EPTFE structure wasrestrained to prevent shrinkage and was allowed to dry at approximately23° C. overnight.

The EPTFE/perfluoro ion exchange polymer composite was wet with a 0.1%tetraethylammonium perfluorooctane sulfonate solution in water toevaluate liquid permeability.

The resulting composite diaphragm contained approximately 5.5% perfluorosulfonic acid polymer by weight and had a permeability of 0.085reciprocal hours to 0.1% tetraethylammonium perfluorooctane sulfonate inwater when measured at 23° C. and at a 20 cm head height differential.

The diaphragm was installed in a laboratory cell while wet with thesurfactant/water solution and tested as described in Example 2. Membranequality brine was allowed to flow through the diaphragm without appliedcurrent overnight. The current was started and increased to 11.25amperes over a five-minute period. The initial cell voltage at fullcurrent was 2.76 volts. After five days on load, the cell was producinga 9.6% caustic at 2.99 volts with a current efficiency at 90.2%. Theanolyte head was 57 centimeters. The cell test was then terminated.

EXAMPLE 5 (COMPARATIVE)

A section of expanded PTFE sheeting, the same as in Example 4, with anaverage methanol bubble point of 11.8 psi (ASTM F316-80), an air flow ofapproximately 5.1 seconds as measured by Gurley Densometer (ASTMD726-58) and thickness of approximately 4.4 mil was wound onto analuminum mandrel (6" o.d. and 9" in length). A total of twenty layers ofEPTFE sheeting were wound onto the mandrel. This sheeting was restrainedby placing hose clamps around the circumference of the mandrel at eachend. The layers of EPTFE sheeting were bonded together by immersing thewound mandrel in a molten salt bath at 370° C. for one minute. The EPTFEwound mandrel was then allowed to cool slowly in room temperature air.

The layered EPTFE was cut along the length of the mandrel and removed toform a flat sheet. A section of this layered EPTFE sheet was wet withisopropyl alcohol and placed in a permeability apparatus. The high headchamber of the cell was quickly filled with 0.1% tetraethylammoniumperfluorooctane sulfonate in water and this solution was allowed to flowthrough the sample and displace the isopropyl alcohol. After the samplewas fully wet with solution, permeability was measured.

The resulting diaphragm was 65 mils thick, had a Gurley air flow of 97sec. and a permeability of 0.448 reciprocal hours to 0.1%tetraethylammonium perfluorooctane sulfonate in water when measured at23° C. and at a 20 cm head height differential. This diaphragm samplecontained no perfluoro ion exchange polymer.

The diaphragm was installed in a laboratory cell while wet with thesurfactant/water solution and tested as described in Example 2. Membranequality brine was allowed to flow through the diaphragm overnightwithout applied current. The current was started and increased to 11.25amperes over a two-minute period. The initial cell voltage at fullcurrent was 3.01 volts. After one day on line, the cell was producing8.8% caustic at 3.01 volts with a current efficiency of 90.1%. Duringthe next 8 hours, the cell overvoltaged, shutting off the current supplyto the cell. The cell could not be restarted.

EXAMPLE 6

A section of expanded PTFE sheeting having an average methanol bubblepoint of 8.42 psi (ASTM F316-80), an air flow of approximately 4 secondsas measured by Gurley Densometer (ASTM D726-58) and thickness ofapproximately 3.8 mil was wound onto an aluminum mandrel (19" o.d. and20" in length). A total of eighteen layers of EPTFE sheeting were woundonto the mandrel. This sheeting was restrained by placing hose clampsaround the circumference of the mandrel at each end. The layers of EPTFEsheeting were bonded together by immersing the wound mandrel in a moltensalt bath at 365° C. for one minute. The EPTFE wound mandrel was thenallowed to cool slowly in room temperature air.

The layered EPTFE was cut along the length of the mandrel and removed toform a flat sheet. A section of this layered EPTFE sheet was impregnatedwith a liquid composition comprising 3.3% perfluoro sulfonic acidpolymer (equivalent weight 920 to 950), as in Example 2, 0.4% TritonX-100 non-ionic surfactant (Rohm and Haas), 0.1% Triton CF-54 non-ionicsurfactant (Rohm and Haas) and 0.6% tetraethylammonium perfluorooctanesulfonate in ethyl alcohol. The wet layered EPTFE structure wasrestrained to prevent shrinkage and was allowed to dry at approximately23° C. overnight and then baked at 100° C. for 7 minutes.

The resulting composite diaphragm was approximately 65 mils thick, had aGurley air flow of 85 sec. and a permeability of 0.653 reciprocal hoursto 0.1% tetraethylammonium perfluorooctane sulfonate in water whenmeasured at 23° C. and at a 20 cm head height differential.

The diaphragm was installed in a laboratory cell while dry and tested asdescribed in Example 2. Water was fed to the anolyte compartment forfour hours. The water feed was stopped and membrane quality brine wasallowed to flow through the diaphragm over a two-day period withoutapplied current. During four days of operation on membrane qualitybrine, the cell produced an average of 9.5% caustic at an average cellvoltage of 2.95 volts. The average caustic current efficiency was 91.2%,and energy consumption was 2168 kilowatt hours per metric ton ofcaustic. The anolyte head was steady at about seven centimeters. Thebrine feed to the cell was then switched to diaphragm quality brine.Over the next twenty days of operation, the cell produced an average of9.9% caustic at an average of 3.26 volts. The caustic current efficiencyaveraged 94.9% and the energy consumption was 2304 kilowatt hours permetric ton of caustic during the period operated on this brine. The cellwas terminated after a total of 27 days on line. The anolyte head was 62centimeters when cell operation was terminated.

EXAMPLE 7

A section of expanded PTFE sheeting having an average methanol bubblepoint of 7.0 psi (ASTM F316-80), an air flow of approximately 4 secondsas measured by Gurley Densometer (ASTM D726-58) and thickness ofapproximately 4 mils was wound onto an aluminum mandrel (3.5" o.d. and9" in length). A total of twenty layers of EPTFE sheeting were woundonto the mandrel. This sheeting was restrained by placing hose clampsaround the circumference of the mandrel at each end. The layers of EPTFEsheeting were bonded together by immersing the wound mandrel in a moltensalt bath at 370° for one minute. The EPTFE wound mandrel was thenallowed to cool slowly in room temperature air.

The layered EPTFE was cut along the length of the mandrel and removed toform a flat sheet. A section of this layered EPTFE sheet was impregnatedwith a liquid composition comprising 3.75% perfluoro sulfonic acidpolymer (equivalent weight 920 to 950), as in Example 2, 1.2% TritonX-100 non-ionic surfactant (Rohm and Haas) and 0.4% Triton CF-54non-ionic surfactant (Rohm and Haas) in ethyl alcohol. The wet layeredEPTFE structure was restrained to prevent shrinkage and was allowed todry at approximately 23° C. overnight. The composite was then baked at80° C. for five minutes.

The EPTFE/perfluoro ion exchange polymer composite was wet with a 0.1%tetraethylammonium perfluorooctane sulfonate solution in water toevaluate liquid permeability.

The resulting composite diaphragm contained 13.7% perfluoro sulfonicacid polymer by weight and had a permeability of 0.565 reciprocal hoursto 0.1% tetraethylammonium perfluorooctane sulfonate in water whenmeasured at 23° C. and at a 20 cm head height differential.

The diaphragm was installed in a laboratory cell while wet with thesurfactant/water solution and tested as described in Example 2. Membranequality brine was allowed to flow through the diaphragm overnightwithout applied current. Over one hundred and twenty-one days ofoperation on membrane quality brine, the cell produced an average of10.2% caustic at an average cell voltage of 3.17 volts. The averagecaustic current efficiency was 95.1% and energy consumption was 2231kilowatt hours per metric ton of caustic. The anolyte head was steady atabout six centimeters. The brine feed was then switched to a batch ofbrine which was contaminated with particulates. This resulted in partialplugging of the diaphragm; cell operation degenerated and wasterminated.

EXAMPLE 8

A section of expanded PTFE sheeting having an average methanol bubblepoint of 11.8 psi (ASTM F316-80), an air flow of approximately 5.1seconds as measured by Gurley Densometer (ASTM D726-58) and thickness ofapproximately 4.4 mils was wound onto an aluminum mandrel (3.5" o.d. and9" in length). A total of seventeen layers of EPTFE sheeting were woundonto the mandrel. This sheeting was restrained by placing hose clampsaround the circumference of the mandrel at each end. The layers of EPTFEsheeting were bonded together by immersing the wound mandrel in a moltensalt bath at 370° C. for one minute. The EPTFE wound mandrel was thenallowed to cool slowly in room temperature air.

The layered EPTFE was cut along the length of the mandrel and removed toform a flat sheet. A section of this layered EPTFE sheet was impregnatedwith a liquid composition comprising 2.7% perfluoro sulfonic acidpolymer (equivalent weight 920 to 950), as in Example 2, 0.9% TritonX-100 non-ionic surfactant (Rohm and Haas) and 0.3% Triton CF-54non-ionic surfactant (Rohm and Haas) in ethyl alcohol. The wet layeredEPTFE structure was restrained to prevent shrinkage and was allowed todry at approximately 23° C. overnight. The composite was then baked at100° C. for 5 minutes.

The EPTFE/perfluoro ion exchange polymer composite was wet with a 0.1%tetraethylammonium perfluorooctane sulfonate solution in water toevaluate liquid permeability.

The resulting composite diaphragm contained 6.0% perfluoro sulfonic acidpolymer by weight and had a permeability of 0.490 reciprocal hours to0.1% tetraethylammonium perfluorooctane sulfonate in water when measuredat 23° C. and at a 20 cm head height differential.

The sample described above was installed wet in a laboratory cell andtested as described in Example 2. Membrane brine was fed to the anodecompartment overnight before current was applied. Over the first 35 daysof operation, the cell voltage averaged 2.99 volts, the currentefficiency was 95.0% and the caustic concentration was 10.3%. During thenext 10 days, problems with the brine feed system caused the causticconcentration to increase to 18.4%, then decrease to 8.8% before thecell was stabilized again. For the next 60 days, the cell voltageaveraged 3.10 volts, the current efficiency was 95.1% and causticconcentration was 9.7%. The cell was allowed to operate for a total of186 days, during the last 85 of which the cell operated at an averagecell voltage of 3.10 volts, an average current efficiency of 94.7% andan average caustic concentration of 9.9%. Overall, excluding the ten daycaustic excursion, the cell operated at an average of 3.07 volts, 94.9%current efficiency and 9.9% caustic. These results are summarized inTable 3.

                  TABLE 3                                                         ______________________________________                                               Caustic          Cell  kWh/    k factor                                Days   wt. %    CE %    Volts MT NaOH V/(kA/m.sup.2)                          ______________________________________                                         1-35  10.3     95.0    2.99  2110    0.28                                    36-45  caustic excursion to 18.4%                                              46-105                                                                              9.7      95.1    3.10  2180    0.32                                    105-186                                                                              9.9      94.7    3.10  2190    0.32                                    Avg.   9.9      94.9    3.08  2170    0.31                                    (excluding caustic excursion)                                                 ______________________________________                                    

EXAMPLE 9

A section of expanded PTFE sheeting with an average methanol bubblepoint of 9.9 psi (ASTM F316-80), an air flow of approximately 6 secondsas measured by Gurley Densometer (ASTM D726-58) and thickness ofapproximately 4.5 mils was wound onto an aluminum mandrel (19" o.d. and21" in length). A total of twenty-two layers of EPTFE sheeting werewound onto the mandrel. This sheeting was restrained by placing hoseclamps around the circumference of the mandrel at each end. The layersof EPTFE sheeting were bonded together by immersing the wound mandrel ina molten salt bath at 370° C. for one minute. The EPTFE wound mandrelwas then allowed to cool slowly in room temperature air.

The layered EPTFE was cut along the length of the mandrel and removed toform a flat sheet. A section of this layered EPTFE sheet was impregnatedwith a liquid composition comprising 3.3% perfluoro sulfonic acidpolymer (equivalent weight 920 to 950), as in Example 2, 0.4% TritonX-100 non-ionic surfactant (Rohm and Haas), 0.1% Triton CF-54 non-ionicsurfactant (Rohm and Haas) and 0.6% tetraethylammonium perfluorooctanesulfonate (Mobay) in ethyl alcohol. The wet layered EPTFE structure wasrestrained to prevent shrinkage and was allowed to dry at approximately23° C. overnight. The composite was then baked at 100° C. for 7 minutes.

The resulting composite diaphragm was approximately 80 mils thick, had aGurley air flow of 95 seconds and a permeability of 0.366 reciprocalhours to 0.1% tetraethylammonium perfluorooctane sulfonate in water whenmeasured at 23° C. and at a 20 cm head height differential.

The sample described above was installed dry in a laboratory cell andtested as described in Example 2. The anolyte compartment was filledwith water and the water was allowed to flow through the diaphragm forseveral hours. Membrane quality brine feed was then started and allowedto flow for several hours before the current was applied. Over the firsttwo days of operation, the average cell voltage was 2.99 volts andcurrent efficiency was 94.0% at 10.2% caustic with a 21 centimeteranolyte head. The brine feed was then switched to diaphragm qualitybrine. Over the next 38 days, there was a steady increase in anode headand voltage. The average cell voltage over this time period was 3.13volts and current efficiency was 93.1% at 10.1% caustic production and a32 cm anolyte head. After the head and voltage stabilized, the cell wasoperated for 381 more days, for a total of 421 days of operation. Duringthis time, it experienced numerous shutdowns, caustic excursions andother upsets. Overall, during these 381 days, the cell produced anaverage of 9.9% caustic, at an average cell voltage of 3.25 volts, anaverage current efficiency of 94.7% and an anolyte head of 28centimeters. These results are summarized in Table 4.

                  TABLE 4                                                         ______________________________________                                               Caustic          Cell  kWh/    k factor                                Days   wt. %    CE %    Volts MT NaOH V/(kA/m.sup.2)                          ______________________________________                                        1-2    10.2     94.0    2.99  2130    0.28                                    2-40   10.1     93.1    3.13  2350    0.33                                    41-421  9.9     94.7    3.25  2300    0.38                                    ______________________________________                                    

EXAMPLE 10

A section of expanded PTFE sheeting having an average methanol bubblepoint of 10.5 psi (ASTM F316-80), an air flow of 11 seconds as measuredby Gurley Densometer (ASTM D726-58) and a 4.5 mils thickness was woundaround an aluminum mandrel (6.0" o.d. and 9" in length). Eight layers ofthis sheeting were wound onto the mandrel. Then a section of expandedPTFE sheeting with an average methanol bubble point of 7.1 psi (ASTMF316-80), an air flow of 5 seconds as measured by Gurley Densometer(ASTM D726-58) and a thickness of 4 mils was wound on top of it.Seventeen layers of this sheeting were wound over the initial eightlayers.

The EPTFE sheeting was restrained by placing hose clamps around thecircumference of the mandrel at each end. The layers of EPTFE werebonded together by immersing the wound mandrel in a molten salt bath at367° C. for one minute. The EPTFE wound mandrel was allowed to coolslowly in room temperature air. The exposed outer surface of the EPTFEwhich had been derived from the precursor with the lower methanol bubblepoint is herein designated side A. The reverse side is herein designatedas side B.

The layered EPTFE structure was impregnated with a liquid composition of3.3% perfluoro sulfonic acid polymer (equivalent weight 920 to 950), asin Example 2, 0.4% Triton X-100 non-ionic surfactant (Rohm and Haas),0.1% Triton CF-54 non-ionic surfactant (Rohm and Haas) and 0.6%tetraethylammonium perfluorooctane sulfonate in ethyl alcohol. The wetEPTFE structure was restrained to prevent shrinkage and was allowed todry at 23° C. for 16 hours. The restrained EPTFE/perfluoro ion exchangepolymer composite was then placed into a 100° C. oven for 7 minutes forfinal drying.

A strip 0.248 inches wide and 6 cm long and 0.089 inches thick was cutfrom the dried composite structure (thickness and width figures wereeach the average of three measurements along the 6 cm length). The stripwas weighed and density calculated. A razor incision was then made atone end of the strip in a plane parallel to the surface (i.e.,perpendicular to the Z axis or thickness direction). The separation waspropagated by peeling one section from the other; the multilayerstructure being delaminated at the interface between two discreteprecursor layers. The section containing the A side is herein designatedsection AS. The section containing the B side is herein designated BS.Thickness (the average of three measurements along the 6 cm length) andweight of each section was measured and the density of each section wascalculated. Results are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                                   Thickness (inches)                                                                       Density (gm/cc)                                         ______________________________________                                        Composite structure                                                                        0.89         .350                                                AS section   0.42         .308                                                BS section   0.47         .388                                                ______________________________________                                    

These measurements demonstrate the asymmetry with respect to density andstructure which can be achieved by this invention.

A sample of EPTFE/perfluoro ion exchange polymer composite prepared asabove was then wet with a solution of 0.1% tetraethylammoniumperfluorooctane sulfonate in water to evaluate liquid permeability.Permeability was measured with a 20 cm head of water containing 0.1%tetraethylammonium perfluorooctane sulfonate at 23° C. No measurementswere taken until excess surfactant had been flushed from the diaphragmas evidenced by the diaphragm becoming uniformly translucent with noopaque or hazy regions. With the sample oriented in the permeabilitytester with flow in the direction from the A side, through the diaphragmtowards the B side, the permeability measured was 0.20 reciprocal hours.

A sample of the composite described above was installed dry in alaboratory cell with the A side oriented towards the anode. Water wasfed to the anode compartment for two hours, then the feed was changed tomembrane quality brine which continued overnight before power wasapplied. The cell was operated for 11 days producing an average of 9.9%caustic. The cell voltage averaged 3.01 volts and the current efficiencywas 94.2%, for a total electrical energy consumption of 2140 kilowatthours per metric ton of caustic. The cell was shut down for maintenanceto the laboratory area, and the diaphragm was damaged when the cell wasrestarted. Results are summarized in Table 6.

                  TABLE 6                                                         ______________________________________                                             Caustic          Cell    kWh/    k factor                                Days wt. %    CE %    Volts   MT NaOH V/(kA/m.sup.2)                          ______________________________________                                        1-11 9.9      94.2    3.01    2140    0.28                                    ______________________________________                                    

EXAMPLE 11

A section of expanded PTFE sheeting having an average methanol bubblepoint of 10.5 psi (ASTM F316-80), an air flow of 11 seconds as measuredby Gurley Densometer (ASTM D726-58) and a 4.5 mil thickness was woundaround an aluminum mandrel (33/8" o.d. and 9" in length). Nine layers ofthis sheeting were wound onto the mandrel. Then a section of expandedPTFE sheeting having average methanol bubble point of 6.3 psi (ASTMF316-80), an air flow of 5 seconds as measured by Gurley Densometer(ASTM D726-58), and a thickness of 3.7 mils was wound on top of it.Seventeen layers of this sheeting were wound over the initial ninelayers.

The EPTFE sheeting was restrained by placing hose clamps around thecircumference of the mandrel at each end. The layers of EPTFE werebonded together by immersing the wound mandrel in a molten salt bath at364° C. for one minute. The exposed outer surface of the EPTFE which hadbeen derived from the precursor with the lower methanol bubble point isherein designated as side A. The reverse side is herein designated asside B.

The layered EPTFE structure was impregnated with a liquid composition of3.3% perfluoro sulfonic acid polymer (equivalent weight 920 to 950), asin Example 2, 0.4% Triton X-100 non-ionic surfactant (Rohm and Haas),0.1% Triton CF-54 non-ionic surfactant (Rohm and Haas) and 0.6%tetraethylammonium perfluorooctane sulfonate in ethyl alcohol. The wetEPTFE structure was restrained to prevent shrinkage and was allowed todry at 23° C. for 16 hours. The restrained EPTFE/perfluoro ion exchangepolymer was then placed into a 100° C. oven for 7 minutes for finaldrying.

A strip 0.249 inches wide and 6 cm long and 0.071 inches thick was cutfrom the dried composite structure. Thickness and width figures wereeach the average of three measurements along the 6 cm length. The stripwas weighed and density calculated. A razor incision was then made atone end of the strip in a plane parallel to the surface (i.e.,perpendicular to the Z axis or thickness direction). The separation waspropagated by peeling one section from the other, the multilayerstructure being delaminated at the interface between the two discreteprecursor layers. The section containing the A side is herein designatedsection AS. The section containing the B side is herein designatedsection BS. Thickness (the average of three measurements along the 6 cmlength) and weight of each section was measured and the density of eachsection calculated. Results are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                                   Thickness (inches)                                                                       Density (gm/cc)                                         ______________________________________                                        Composite structure                                                                        .071         .403                                                AS section   .024         .346                                                BS section   .047         .433                                                ______________________________________                                    

The composite laminate as described was installed dry in a laboratorycell with the A side oriented towards the anode. Deionized water wasslowly fed into the anolyte compartment until the cell was filled, andthen was allowed to flow through the diaphragm for two more hours. Thedeionized water feed was stopped and membrane quality brine feed wasstarted to the cell overnight before current was applied. After one dayof operation, the cell voltage was 3.20 volts, declining to 3.12 voltson the second day. Over the first nine days of operation, the averagecell voltage was 3.13 volts and average current efficiency was 96.7% at10.2% caustic. The average electrical energy consumption during thisperiod was 2170 kilowatt hours per metric ton of caustic produced.Between the eleventh and twelfth days on line, the brine feed stoppeddue to a salt blockage, and the cell ran without feed for anundetermined amount of time. After the brine feed was restarted and thecell was allowed to equilibrate overnight, the cell voltage was 3.20volts. Over the next seven days, the voltage slowly decreased to 3.11volts. Overall, from days thirteen to twenty, the cell produced anaverage of 10.1% caustic with an average cell voltage of 3.14 volts andan average current efficiency of 96.2%. This corresponds to anelectrical energy consumption of 2190 kilowatt hours per metric toncaustic. Results are summarized in Table 8.

                  TABLE 8                                                         ______________________________________                                              Caustic         Cell    kWh/    k factor                                Days  wt. %   CE %    Volts   MT NaOH V/(kA/m.sup.2)                          ______________________________________                                        1-9   10.2    96.7    3.13    2170    0.33                                    Brine feed blockage: high caustic production                                  13-27 10.0    96.5    3.14    2180    0.34                                    ______________________________________                                    

EXAMPLE 12

A section of expanded PTFE sheeting having an average methanol bubblepoint of 10.3 psi (ASTM F316-80), an air flow of 6 seconds as measuredby Gurley Densometer (ASTM D726-58) and a 2.9 mil thickness was woundaround an aluminum mandrel (3.5" o.d. and 9" in length). Eleven layersof this sheeting were wound onto the mandrel. Then a long section ofexpanded PTFE sheeting with an average methanol bubble point of 6.3 psi(ASTM F316-80), an air flow of 5 seconds as measured by GurleyDensometer (ASTM D726-58), and a thickness of 3.7 mils was wound on topof it. Fifteen layers of this sheeting were wound over the initialeleven layers.

The EPTFE sheeting was restrained by placing hose clamps around thecircumference of the mandrel at each end. The layers of EPTFE werebonded together by immersing the wound mandrel in a molten salt bath at370° C. for one minute. The EPTFE wound mandrel was allowed to coolslowly in room temperature air. The exposed outer surface of the EPTFEwhich had been derived from the precursor with the lower methanol bubblepoint is herein designated as side A. The reverse side is hereindesignated as side B.

The layered EPTFE structure was impregnated with a liquid composition of3.2% perfluoro sulfonic polymer (equivalent weight 920 to 950), as inExample 2, 0.75% Triton X-100 non-ionic surfactant (Rohm and Haas),0.25% Triton CF-54 non-ionic surfactant (Rohm and Haas) and 1%tetraethylammonium perfluorooctane sulfonate in ethyl alcohol. The wetEPTFE structure was restrained to prevent shrinkage and was allowed todry at 23° C. for 16 hours. The restrained EPTFE/perfluoro ion exchangepolymer composite was then placed into a 100° C. oven for 7 minutes as afinal treatment. The dried structure was 68 mils in thickness.

The EPTFE/perfluoro ion exchange polymer composite was wet with asolution of 0.1% tetraethylammonium perfluorooctane sulfonate in waterto evaluate liquid permeability. Permeability was measured with a 20 cmhead of water containing 0.1% tetraethylammonium perfluorooctanesulfonate at 23° C. No measurements were taken until excess surfactanthad been flushed from the diaphragm as evidenced by the diaphragmbecoming uniformly translucent with no opaque or hazy regions; thisrequired about 1 hour. With the sample oriented in the permeabilitytester with flow in the direction from A side through the diaphragmtowards the B side, the permeability measured was 0.42 reciprocal hours.

The sample as described above was installed wet in a laboratory cellwith the A side oriented towards the anode. Membrane quality brine wasfed to the anode compartment for 70 minutes before current was applied.Over the first two days of operation, the diaphragm performed with acell voltage of 3.12 volts and a current efficiency of 91.8% at 9.9%caustic. The brine feed was then changed to diaphragm quality brine, andthe cell operated for 3 days before it was shut down for several hoursfor cell room repairs. The cell was restarted and allowed to operate for27 more days, for a total of 30 days on diaphragm quality brine. Overthis time, the average cell voltage was 3.31 volts and the currentefficiency was 93.6% while producing an average of 10.1% caustic. Theaverage electrical energy consumption was 2370 kilowatt hours per metricton of caustic. At the end of these 32 days, the anolyte head was 29centimeters. The cell failed due to electrical problems at 35 days online, and the diaphragm was damaged when restart was attempted. Theresults are summarized in Table 9.

                  TABLE 9                                                         ______________________________________                                             Caustic          Cell    kWh/    k factor                                Days wt. %    CE %    Volts   MT NaOH V/(kA/m.sup.2)                          ______________________________________                                        1-2   9.9     91.8    3.12    2280    0.33                                    3-32 10.1     93.6    3.31    2370    0.40                                    ______________________________________                                    

EXAMPLE 13

A section of expanded PTFE sheeting with an average methanol bubblepoint of 11.8 psi (ASTM F316-80), an air flow of 5.1 seconds as measuredby Gurley Densometer (ASTM D726-58) and a 4.4 mil thickness was woundaround an aluminum mandrel (3.5" o.d. and 9" in length). Eleven layersof this sheeting were wound onto the mandrel.

The EPTFE sheeting was restrained by placing hose clamps around thecircumference of the mandrel at each end. The layers of EPTFE werebonded together by immersing the wound mandrel in a molten salt bath at370° C. for one minute. The EPTFE wound mandrel was allowed to coolslowly in room temperature air.

The layered EPTFE structure was impregnated with a liquid composition of3.2% perfluoro sulfonic acid (equivalent weight 920 to 950), as inExample 2, 1.2% Triton X-100 non-ionic surfactant (Rohm and Haas) and0.4% Triton CF-54 non-ionic surfactant (Rohm and Haas) in ethyl alcohol.The wet EPTFE structure was restrained to prevent shrinkage and wasallowed to dry at 23° C. for 16 hours. The restrained EPTFE/perfluoroion exchange polymer composite was then placed in a 100° C. oven forfive minutes as final treatment.

A 1.4% solution of perfluorocarboxyl ester polymer in1,1,2-trichloro-1,2,2-trifluoroethane (Freon TF®, DuPont) was applied toone side of the restrained EPTFE/perfluoro ion exchange polymercomposite and the composite was allowed to dry at room temperature forone hour. The perfluorocarboxyl ester used was a copolymer oftetrafluoroethylene and ##STR11## with an equivalent weight in the freeacid form of approximately 650 to 750. The treated side is hereindesignated side C. The composite was wet with a 36% potassium hydroxidesolution in a mixture of 85% water and 15% isopropanol and allowed toreside in this solution for 16 hours at room temperature to hydrolyzethe perfluoro carboxyl ester polymer to the potassium ion form of theperfluorocarboxylate polymer. The impregnated structure was thenimmersed in a bath of 0.1% tetraethylammonium perfluorooctane sulfonatein water for one hour to dilute and largely replace residual potassiumhydroxide solution in the pores. The resultant composite (on a drybasis) contained about 9% perfluorosulfonic acid polymer and about 0.9%perfluorocarboxylic acid polymer, the latter being largely concentratedon side C. Permeability was then measured with a 20 cm head of watercontaining 0.1% tetraethylammonium perfluorooctane sulfonate at 23° C.No measurements were taken until excess surfactant had been flushed fromthe diaphragm as evidenced by the diaphragm becoming uniformlytranslucent with no opaque or hazy regions. The permeability measuredwas 0.23 reciprocal hours.

The diaphragm was installed in a laboratory cell while wet with thesurfactant/water solution from the permeability apparatus with the sidedesignated side C oriented towards the cathode. Membrane quality brinewas allowed to flow through the diaphragm overnight without appliedcurrent. The current was started and increased to 11.25 amperes over aten-minute period. The initial cell voltage at full current was 2.91volts. Over seventeen days on load, the cell produced an average of10.0% caustic at an average cell voltage of 2.97 volts. The averagecaustic current efficiency was 91.5% and electrical energy consumptionwas 2176 kilowatt hours per metric ton of caustic. The anolyte head wassteady at about 12 centimeters.

EXAMPLE 14

A section of expanded PTFE sheeting having an average methanol bubblepoint of 8.4 psi (ASTM F316-80), an air flow of 4 seconds as measured byGurley Densometer (ASTM D726-58) and a 3.8 mil thickness was woundaround an aluminum mandrel (3.5" o.d. and 9" in length). Five layers ofthis sheeting were wound onto the mandrel. Then a section of expandedPTFE sheeting with an average methanol bubble point of 26.0 psi (ASTMF316-80), an air flow of 3.5 seconds as measured by Gurley Densometer(ASTM D726-58) and a thickness of 1.1 mils was wound around the firstsheeting. Four layers of this second sheeting were wound over theinitial five layers.

EPTFE sheeting was restrained by placing hose clamps around thecircumference of the mandrel at each end. The layers of EPTFE werebonded together by immersing the wound mandrel in a molten salt bath at365° C. for one minute. The EPTFE wound mandrel was allowed to coolslowly in room temperature air. The exposed outer surface of the EPTFEwhich had been derived from the precursor with the higher methanolbubble point is herein designated side A.

The layered EPTFE structure was impregnated with a liquid composition of3.3% perfluoro sulfonic acid polymer (equivalent weight 920 to 950),0.4% Triton X-100 non-ionic surfactant (Rohm and Haas), 0.1% TritonCF-54 non-ionic surfactant (Rohm and Haas) and 0.6% tetraethylammoniumperfluorooctane sulfonate in ethyl alcohol. The wet EPTFE structure wasrestrained to prevent shrinkage and was allowed to dry at 23° C. for 16hours. The restrained EPTFE/perfluoro ion exchange polymer composite wasthen placed into a 100° C. oven for 7 minutes for final drying.

The resulting composite was approximately 17 mil thick, had a Gurley airflow of 56 seconds and a density of 0.322 g/cc.

A 2-inch diameter disk of the composite was placed in a filter holder ona vacuum flask and connected to a vacuum pump. The composite disk wasinstalled so that the A side faced the high pressure side. A 1%suspension of fumed silica in deionized water was directed to the A sideof the composite and the vacuum pump turned on.

Approximately 25 milliliters of the 1% fumed silica suspension wasfiltered. The filtrate appeared clear and free of turbidity. A singledrop of filtrate was placed on a clean glass slide and dried. Similarly,a single drop of the 1% suspension was placed on a clean glass slide anddried. Both of these samples were examined under high magnification(100,000×) using a scanning electron microscope. The fumed silicasuspension specimen showed very small spherical particles, approximately200 Angstroms in diameter, and agglomerates of these particles. Thefiltrate specimen was virtually free of the fumed silica particles. Thisdemonstrates that this composite is a very effective filter for evenvery small particles.

EXAMPLE 15

A section of expanded PTFE sheeting having an average methanol bubblepoint of 25 psi (ASTM F316-80), an air flow of 13.4 seconds as measuredby Gurley densometer (ASTM D726-58) and a thickness of 1.5 mils waswound onto a stainless steel mandrel (14.0" o.d. and 40.0" in length).Twenty layers of this sheeting were wound onto the mandrel. Then asection of expanded PTFE sheeting having an average methanol bubblepoint of 16.5 psi (ASTM F316-80) an air flow of 13.5 sec. as measured byGurley densometer (ASTM D726-58) and a thickness of 4.8 mils was woundon top of the previous layers. Twenty-nine layers of this second type ofsheeting were wound over the initial twenty layers.

The EPTFE sheeting was restrained by placing hose clamps around thecircumference of the mandrel at each end. The layers of EPTFE werebonded together by immersing the wound mandrel in a molten salt bath at370° C. for two minutes. The EPTFE wound mandrel was allowed to coolslowly in room temperature air. Then the cylindrical tube was cutlongitudinally and removed from the mandrel to form a flat sheet. Theexposed outer surface of the EPTFE which had been derived from thepresursor with the lower methanol bubble point is herein designated sideA. The reverse side is herein designated as side B.

The layered EPTFE structure was restrained in a frame and placed in avacuum chamber with side B facing up. Vacuum was drawn in the chamber to125 mm Hg, absolute pressure. While maintaining vacuum, a liquidcomposition of 3.3% perfluorosulfonic acid polymer (equivalent weight600-700, extracted from 900-950 EW polymer using CF₂ ClCFCl₂ at reflux),1.5% Triton X-100 non-ionic surfactant (Rohm & Haas), 0.5% Triton CF-54non-ionic surfactant (Rohm & Haas) and 10% 1-methoxy-2-propanol in ethylalcohol was introduced to the B side of the EPTFE sheet. The liquidcomposition was allowed to fully wet the layered EPTFE sheeting whileunder 125 mm Hg, absolute pressure vacuum. After impregnation the vacuumwas released, excess liquid composition was removed from the EPTFEstructure surface and the structure was allowed to dry (A side down) for16 hours at 23° C. The restrained EPTFE/perfluoro ion exchange polymercomposite was then placed into a 100° C. oven for 7 minutes for finaldrying.

The resulting composite diaphragm was approximately 121 mils inthickness, had a Gurley air flow of 612 sec. and a specific gravity of0.61.

The diaphragm was installed in a laboratory cell while dry and tested asdescribed in Example 2, with side B oriented toward the cathode. Waterwas fed to the anolyte compartment for 16 hours. The water feed wasstopped and membrane quality brine was allowed to flow through thediaphragm for 5 to 6 hours before current was applied. During 56 days ofoperation on membrane quality brine at 85° C. and 2.5 kA/m², the cellproduced an average of 10.0% caustic at an average cell voltage of 3.10volts. This corresponds to a k-factor of 0.32 Vm² /kA. The averagecaustic current efficiency was 95.2%, and energy consumption was 2182kilowatt hours per metric ton of caustic. The anolyte head was steady atabout 23 centimeters. Repeats of this example gave essentially identicalresults.

Comparison of Cell Performance Between Conventional Diaphragms and thePresent Invention

diaphragm production of chlorine and caustic is typically carried outusing a slurry-deposited diaphragm made of asbestos fiber or resinbonded asbestos fiber (modified asbestos). This type of asbestosdiaphragm has been used in the industry for a number of years. Cellperformance of a typical modified asbestos diaphragm is given by DonaldL. Caldwell on page 140 of Chapter 2 of "Comprehensive Treatise ofElectrochemistry, Volume 2: Electrochemical Processing", edited byBockris, Conway, Yeager and White, Plenum Press, New York and London,1981. Summarizing Caldwell's data at current densities at or around 2kA/m², current efficiencies ranged from 95.4% to 97.8% and k factorsranged from 0.48 to 0.63 Vm² /kA for different commercial cells. Foroperation at 2.5 kA/m² as in our examples, the cell voltages could beexpected to be between about 3.50 and 3.87 volts, resulting in powerconsumption values ranging from 2440 to 2700 kilowatt hours per metricton of caustic. These data were taken from cells using a version ofresin bonded asbestos diaphragms.

The diaphragm of the present invention has exhibited better cellperformance than modified asbestos diaphragms. Conservative estimates ofcell performance of this diaphragm give about 95% current efficiency, ak factor of 0.32 to 0.34 Vm² /kA and a cell voltage of 3.13 volts at acurrent density of 2.5 kA/m², all equating to a power consumption of2208 killowatt hours per metric ton of NaOH, an improvement in powerconsumption of between 9% and 18% from the range quoted above.

Because the asbestos is a fiber made of Mg(OH)₂ and SiO₂, it ispartially soluble in brine depending on pH and is considered a "living"diaphragm.

Caldwell discusses this "living" feature or asbestos diaphragms in thefollowing excerpt:

"Chrysotile asbestos is not chemically stable in chlorine cellelectrolytes Mg(OH)₂ is soluble in acid solutions and stable in basicsolutions; the reverse is true for SiO₂. When a cell is energized, achrysotile diaphragm will become SiO₂ enriched on its acidic, anolyteface, and Mg(OH)₂ enriched on its alkaline, catholyte face. The flowthrough the diaphragm will flush Mg²⁺ ions from the anolyte side towardthe catholyte, where they will reprecipitate as Mg(OH)₂. Thisprecipitate will constrict the flow channels, decreasing flow rate andefficiency and increasing voltage drop and caustic strength. Thediaphragm is said to "tighten". After a period in service, the diaphragmreaches a state of equilibrium with its surroundings and itscharacteristics stabilize. However, any drastic change in operatingconditions will cause the dissolution-reprecipitation process to beginanew".

It is important to note that with each fluctuation in operatingconditions, some portion of the diaphragm is resolubilized and lost.This leads to degradation of the diaphragm and eventual loss ofperformance.

Even with constant operation, the diaphragm is slowly eroded ordissolved so that a steady decrease in current efficiency can beexpected.

The diaphragm of this invention is made of chemically stable materialsand so is insensitive to pH changes, unlike the asbestos diaphragm. ThispH stability allows the diaphragm of this invention to operate underconditions in which electrical upsets occur and in which the currentfluctuates without significant loss of performance. This enables a plantto take advantage of power price breaks at off-peak times (loadshedding) and prevents permanent loss of performance due to electricaloutages. Further, this stability allows cell operators to performchemical treatments to this diaphragm to regenerate performance. All ofthese treatments or changes would be detrimental to an asbestosdiaphragm's performance. Example 2 demonstrates the stability ofperformance of the present invention. Over the course of 421 days ofoperation, which were plagued with numerous electrical upsets thecurrent efficiency remained relatively constant. Examples 8 and 11 alsoillustrate the stability of performance and resiliency of the presentinvention. An asbestos diaphragm, even under the best of operatingconditions, would have shown a steady decline in current efficiency overthis same period of time.

Moreover, an asbestos diaphragm would not have survived the electricalupsets experienced by these examples of the present invention.

For the layered PTFE diaphragm of U.S. Pat. No. 3,944,477, the bestexample of the reference (Example 11) gave a power consumption of 2770kilowatt hours per metric ton of NaOH, surprisingly 25% worse than thetypical 2208 kilowatt hours per metric ton of NaOH of the presentinvention, even though the present invention used a 16% higher currentdensity, which should increase power consumption.

While the invention has been disclosed herein connection with certainembodiments and detailed descriptions, it will be clear to one skilledin the art that modifications or variations of such details can be madewithout deviating from the gist of this invention, and suchmodifications or variations are considered to be within the scope of theclaims hereinbelow.

What is claimed is:
 1. A multilayer, porous, composite, shaped articlecomprising multiple layers of porous, expanded polytetrafluoroethylene(EPTFE) bonded together, said composite, shaped article having at leasta portion of its exterior surfaces and at least a portion of itsinterior pore surfaces coated with a perfluoro ion exchange polymer,said porous, shaped article having open, continuous channelstherethrough which permit flow of fluids through said article.
 2. Thecomposite article of claim 1 having substantially all of its exteriorsurfaces and substantially all of its interior pores coated with aperfluoro ion exchange resin.
 3. The composite article of claim 1containing a water soluble surfactant within its pores.
 4. The compositearticle of claim 1 having a permeability to water containing 0.1% tetraethyl ammonium perfluorooctane sulfonate between about 0.01 and about3.0 reciprocal hours at 23° C. under a 20 cm head of water.
 5. Thecomposite article of claim 1 in which the perfluoro ion exchange polymerhas a ratio of tetrafluoroethylene to functional comonomer of 1.5:1 to5.6:1.
 6. The composite article of claim 1 in which the perfluoro ionexchange polymer is a perfluorosulfonic acid polymer of equivalentweight less than
 1000. 7. The composite article of claim 1 in which theperfluoro ion exchange polymer is a perfluorocarboxylic acid polymer ofequivalent weight less than
 1000. 8. The composite article of claim 1 inwhich the perfluoro ion exchange polymer is a mixture ofperfluorosulfonic acid polymer and perfluorocarboxylic acid polymer ofequivalent weight less than
 1000. 9. The composite article of claim 1 inwhich the perfluoro ion exchange polymer is a copolymer containingperfluorosulfonic acid and perfluorocarboxylic acid groups, with anequivalent weight less than
 1000. 10. The composite article of claim 1in which the percentage by weight of perfluoro ion exchange polymer inthe composite exceeds 2%.
 11. The composite article of claim 1 in theform of a tube.
 12. The composite tube of claim 11 having a wallthickness exceeding 250 micrometers.
 13. The composite article of claim1 in the form of a sheet.
 14. The composite sheet of claim 13 having athickness exceeding 0.25 millimeters.
 15. The composite sheet of claim14 having a thickness between about 0.76 millimeters and about 5.0millimeters.
 16. The composite article of claim 1 having a specificgravity between 0.05 and about 1.1.
 17. The composite article of claim16 having a specific gravity between about 0.15 and about 0.7.
 18. Thecomposite article of claim 1 having an asymmetric fine structure,wherein at least two of said multiple layers have different microporousstructures.
 19. The composite article of claim 18 wherein said at leasttwo layers have methanol bubble point values which differ by at least10%.
 20. The composite article of claim 18 wherein said at least twolayers have specific gravities which differ by at least 10%.
 21. Thecomposite article of claim 18 wherein said at least two layers havespecific gravities which differ by at least 5%.
 22. The compositearticle of claim 21 in the form of a tube and in which said at least twolayers are oriented such that the layer having higher specific gravityis inside the layer having lower specific gravity.
 23. The compositearticle of claim 21 in the form of a tube and in which said at least twolayers are oriented such that the layer having higher specific gravityis outside the layer having lower specific gravity.